Non-corrosive nitrification inhibitor polar solvent formulation

ABSTRACT

This invention relates to stable liquid formulations of the nitrification inhibitor nitrapyrin comprising polar solvents that are stabilized with small amounts of compounds which help to reduce the tendency of polar solutions of nitrapyrin to corrode metal surfaces. Many of the formulations disclosed herein exhibit useful physical, chemical, and bioactive properties including reduced levels of corrosion when in contact with ferrous metals.

RELATED APPLICATIONS

This application claims benefit of U.S. Ser. No. 62/159,884 filed May11, 2015; U.S. Ser. No. 62/159,885, filed May 11, 2015; U.S. Ser. No.62/244,901, filed Oct. 22, 2015; U.S. Ser. No. 62/244,902, filed Oct.22, 2015; and U.S. Ser. No. 62/244,903, filed Oct. 22, 2015, the entirecontents of which are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to relatively non-corrosive, high loadnitrapyrin liquid formulations, comprising polar solvents and novelmetal corrosion inhibitors and method of preparing and using the same.

BACKGROUND AND SUMMARY

(Trichloromethyl)pyridine compounds, such as nitrapyrin(2-chloro-6-(trichloromethyl)pyridine), inhibit the process ofnitrification and have been or are currently used in combination withnitrogen based fertilizers as described in U.S. Pat. No. 3,135,594,which is herein incorporated by reference. The application of thesecompounds helps to maintain levels of ammonium nitrogen applied to thesoil in the ammonium form (plant accessible stabilized nitrogen); higherlevels of plant accessible nitrogen in the soil enhances cropperformance and can increase crop yields.

Due to their volatile nature some formulations of nitrapyrin, alsoreferred to herein as liquid inhibitior compositions, are best appliedby incorporating them mechanically into the soil, or by watering theminto the soil within about 8 hours after applying them to the surface ofthe soil. Some encapsulated formulations of nitrapyrin are suitable forrapid or dump release of nitrapyrin into the soil. Some formulations ofnitrapyrin encapsulated with lignin sulfonates, especially useful forquick release applications, are disclosed in U.S. Pat. No. 4,746,513,which is incorporated herein by reference. Polycondensationencapsulation, as disclosed in U.S. Pat. No. 5,925,464, has also beenused to encapsulate agriculturally active ingredients such asnitrapyrin, particularly to enhance handling safety and storagestability of the active ingredient by using polyurethane rather thanpolyurea encapsulants.

Encapsulated nitrapyrin formulations exhibit certain advantages overliquid non-encapsulated formulations of nitrapyrin, such as improvedstability. Despite the advantages of encapsulated nitrapyrinformulations, liquid non-encapsulated formulations of nitrapyrin arestill used, at least in part, because they tend to be easier toformulate and may cost less than encapsulated nitrapyrin formulations.As with most any soil amendment there is an advantage to usingformulations that include a high level of the agriculturally activecomponent of the formulation. Formulations that have higher levels of anactive ingredient generally mean that less material must be moved,stored, and applied to the field; the net result is that theseformulations may exhibit lower material handling costs.

In most commercially available liquid formulations the level ofnitrapyrin has been limited by the need to pair nitrapyrin withrelatively non-corrosive solvents. Some aspects of the present inventionprovide a liquid formulation of nitrapyrin (i.e., a liquid inhibitorcomposition) that includes a relatively high level of nitrapyrin. Inthese inventive formulations nitrapyrin is present in polar solvents andis especially formulated to be non-corrosive or at least less corrosivethan previous formulations of nitrapyrin that included significantlevels of polar solvents. Dibasic ester, as used herein, refers to acompound containing two ester groups. Examples of dibasic estersinclude, but are not limited to, dimethyl glutarate, dimethyl succinate,dimethyl adipate, dimethyl 2-methylglutarate, and mixtures thereof.

Some embodiments include a liquid formulation of nitrapyrin comprisingof: nitrapyrin, at least one polar solvent selected from the groupconsisting of: (1) N,N-dialkyl fatty acid amides such as those found inproducts such as, but not limited to, di-substituted amides includingfor example N,N-di-methyloctanamide (N,N-dimethylcarprylamide) andN,N-dimethyldecanamide (N,N-dimethylcapramide), compounds sold under thetrade names, Hallcomid M810, Hallcomid M10, still other compounds thatcan be used in capacity include, for example, Rhodiasolv® ADMA 810,Rhodiasolv® ADMA 10, Genagen 4166 and Genagen 4296; (2) cyclohexanone;(3) dibasic esters such as, but not limited to, dimethyl2-methylglutarate, which is available as Rhodiasolv® IRIS, and a dibasicester mixture composed of dimethyl glutarate, dimethyl succinate, anddimethyl adipate which is available as Rhodiasolv® RPDE; (4) glycolethers and polyalkylene diglycol ethers such as, but not limited to,dipropylene glycol methyl ether which is available as Dowanol™ DPM; (5)alkylene carbonates such as, but not limited to, propylene carbonatewhich is available as Jeffsol AG 1555; (6)methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate which is available asRhodiasolv® Polarclean; (7) organophosphate compounds such as, but notlimited to, trialkyl phosphates, (8) alkoxybenzene compounds such as,but not limited to, methoxybenzene (anisole) and ethoxybenzene, (9)ketones such as, but not limited to, cyclopentanone and cyclohexanone,and at least one inhibitor of metal corrosion. The liquid formulationsof the present invention may include high levels of nitrapyrin andexhibit relatively non-corrosive properties, making them suitable foruse with metal objects such as metal storage tanks and metal applicationequipment.

In one embodiment, the corrosion inhibitor is selected from the groupconsisting of: nicotinamide, a picoline, 2,6 lutidine, expoxidizedlinseed oil (ELO) and DER 331 liquid epoxy resin.

In one embodiment, the corrosion inhibitor is niacin, also known asnicotinic acid. In another embodiment, the corrosion inhibitor is aniacin-derivative. In yet another embodiment, the corrosion inhibitor isniacinamide (it is understood that the terms “niacinamide” and“nicotinamide” are synonymous), methyl isonicotinate, niacin esters,acipimox, aluminum nicotinate, niceritrol, nicoclonate, nicomol,inositol hexaniacinate, oxiniacic acid or combinations thereof.

Non-limiting examples of niacin derivatives include methylisonicotinate, niacin esters, niacinamide salicylate, niacinamideascorbate, niacinamide folate, niacinamide lipoate, niacinamide lactate,niacinamide glycolate, niacinamide mandalate, niacinamide malate,niacinamide hydroxycitrate, niacinamide hydroxytetronate, niacinamidealeurate, niacinamide petroselinate, niacinamide pantothenate,niacinamide adenosine monophosphate (AMP), niacinamide diphosphate(ADP), niacinamide adenosine triphosphate (ATP), niacinamidehydroquinone carboxylate, nicotinic acid, niacinamide, Acipimox(5-methylpyrazinecarboxylic acid, 4-oxide), aluminum nicotinate,Niceritrol (3-pyridinecarboxylic acid 2,2-bis[[3-pyridinylcarbonyl]oxy]methyl)-1,3-propanediyl ester, Nicoclonate,Nicomol (2,2,6,6-(1-hydroxycyclohexyl) tetramethyltetrakis(3-pyridinecarboxylate), inositol hexaniacinate, and Oxiniacic Acid(3-pyridinecarboxylic acid, 1-oxide.

In another embodiment, the corrosion inhibitor is derivatized linseedoil, including, but not limited to, epoxidized linseed oil. In anotherembodiment, the corrosion inhibitor is 1,2-epoxydecane. In anotherembodiment, the corrosion is an amino alcohol, for example,2-amino-2-methyl-1-propanol (i.e., AMP-95 or AMP-99). In anotherembodiment, the corrosion inhibitor is an imidazole compound, forexample, 1-methyl imidazole. In another embodiment, the polar solvent isdiethylene glycol butyl ether (DGBE). In another embodiment, thecorrosion inhibitor and/or co-solvent is an esteramide compound.

In yet another embodiment, the corrosion inhibitor is selected fromniacinamide, methyl isonicotinate, niacin esters, acipimox, aluminumnicotinate, niceritrol, nicoclonate, nicomol, inositol hexaniacinate,oxiniacic acid, linseed oil or derivatized linseed oil, including butnot limited to epoxidized linseed oil, 1,2-epoxydecane, an aminoalcohol, for example, 2-amino-2-methyl-1-propanol, 1-methyl imidazole, aquinolone compound such as quinaldine, or any combination thereof.

In another aspect, described herein are liquid fertilizer compositionsfor use in agricultural applications comprising: one more nitrogenousfertilizer compounds; at least one nitrification inhibitor comprising a(trichloromethyl)pyridine compound; a polar solvent; and, optionally, acorrosion inhibitor.

In one embodiment, the liquid inhibitor composition or liquid fertilizercomposition further comprises at least one additional componentincluding, but not limited to, a co-solvent, a pH adjustor, flow agents,preservatives, buffering agents, antifoam agents, compatibility agents,deposition agents, dispersants, drift control agents, penetrants,surfactants, spreaders, and wetting agents, and the like. In oneembodiment, the nitrogenous fertilizer compound is anhydrous ammonia.

Polar solvents that can be used to practice some embodiment of theinvention include, but are not limited to, cyclohexanone, propylenecarbonate, N,N-dialkyl fatty acid amides: specifically the mixture ofC8/C10 fatty acid N,N-dimethylamides (Hallcomid M810), other fatty acidamides also C8 & C10 N,N-dimethylamides individually, the dibasic estermixture composed of dimethyl glutarate, dimethyl succinate, and dimethyladipate, which is available as Rhodiasolv® RPDE, organophosphatecompounds which are trialkyl phosphates, and alkoxybenzene compoundssuch as methoxybenzene (anisole) and ethoxybenzene. In one embodiment,the organophosphate compound may be selected from the group includingtriethyl phosphate, tri(isobutyl)phosphate, tributoxyethyl phosphate(TBEP) and tris(2-ethylhexyl) phosphate. In one embodiment, the polarsolvent is comprised of the dibasic ester mixture composed of dimethylglutarate, dimethyl succinate, and dimethyl adipate (Rhodiasolv® RPDE)and cyclohexanone. In one embodiment, the alkoxybenzene compound ismethoxybenzene (anisole). In one embodiment, the organophosphatecompound is triethyl phosphate.

Polar solvents that have not worked in some of the exemplary formulationdisclosed herein include; (1) dipropylene glycol monomethyl ether(Dowanol DPM), (2) methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate(Polarclean), solvent mixture composed of reaction mass of dimethylglutarate, dimethyl succinate, and dimethyl adipate (Rhodiasolv® RPDE),and N-butylpyrrolidone (TamiSolve NxG).

Corrosion inhibitors that may not be well suited, or even efficacious,for the practice of the instant invention include, methyltrioctylammonium chloride, poly(12-hydroxyoctadecanoic acid-co-ethylenimine)(e.g., Atlox LP6).

Corrosion inhibitors that may be used to practice some embodiments ofthe invention include, for example, pyridinecarboxamides (i.e.,nicotinamide or niacinamide), methylpyridines (i.e., α-picoline, 2,6lutidine), epoxidized seed or vegetable oils (i.e., epoxidized linseedoil (ELO), epoxidized soybean oil, etc.) and epoxy resin (liquidreaction product of epichlorohydrin and bisphenol, such as, D.E.R.™ 331™liquid epoxy resin (DER 331)).

Molecules of the following formulas reduce and/or protect against metalcorrosion caused by certain nitrification inhibitors including thosedisclosed herein, these molecules include:

(1) methylpyridines:

(2) pyridine carboxamides:

(3) pyridine carboxylic acid and esters:

(4) epoxidized seed or vegetable oils:

wherein R₁, R₂, and R₃ independently represent C₁₄-C₂₀ alkyl groupssubstituted with from zero to four epoxide groups;

(5) an epoxy resin based on bisphenol-type chemistry:

wherein R₁ and R₂ independently represent H, C₁-C₄ alkyl, or phenyl, andR₃ and R₄ independently represent H, C₁-C₄ alkyl, C₁-C₄ haloalkyl, orphenyl;

(6) 1,2-epoxyalkanes:

(7) 1-alkylimidazoles:

(8) amine salts of nicotinic acid:

wherein R¹, R² and R³ independently represent H, (C₁-C₁₈) alkyl or(C₁-C₁₈) alkyl substituted with one or more substituents selected from,but not limited to, halogen, hydroxy, alkoxy or alkylthio, provided thatthe substituents are sterically compatible and the rules of chemicalbonding and strain energy are satisfied, or any two of R¹, R² and R³represent —(CH₂)_(n)— where n is an integer from 3-5.

(9) primary, secondary & tertiary amines:

wherein R¹, R² and R³ independently represent H, (C₁-C₁₈) alkyl or(C₁-C₁₈) alkyl substituted with one or more substituents selected from,but not limited to, halogen, hydroxy, alkoxy or alkylthio, provided thatthe substituents are sterically compatible and the rules of chemicalbonding and strain energy are satisfied, or any two of R¹, R² and R³represent —(CH₂)_(n)— where n is an integer from 3-5;

(10) tertiary amine oxides:

wherein R⁴, R⁵ and R⁶ independently represent (C₁-C₁₈) alkyl or (C₁-C₁₈)alkyl substituted with one or more substituents selected from, but notlimited to, halogen, hydroxy, alkoxy or alkylthio, provided that thesubstituents are sterically compatible and the rules of chemical bondingand strain energy are satisfied, or any two of R¹, R² and R³ represent—(CH₂)_(n)— where n is an integer from 3-5, or wherein R⁴ is a straightor branched chain (C₁-C₁₈) alkyl or an alkyletherpropyl oralkylamidopropyl of the formula:

-   -   wherein R⁷ is a straight or branched chain (C₁₀-C₁₈) alkyl, and

R⁵ and R⁶ independently are straight or branched chain (C₁-C₁₈) alkyl orethoxylates or propoxylates of the formula:

wherein n is an integer from 1 to 20;

(11) tetra-substituted ammonium salts:

wherein R¹, R² and R³ independently represents (C₁-C₁₆) alkyl or(C₁-C₁₈) alkyl substituted with one or more substituents selected from,but not limited to, halogen, hydroxy, alkoxy or alkylthio, provided thatthe substituents are sterically compatible and the rules of chemicalbonding and strain energy are satisfied, or any two of R¹, R² and R³represent —(CH₂)_(n)— where n is an integer from 3-5, R⁴ represents((C₁-C₁₆) alkyl or arylalkyl), and X⁻ is selected from, but not limitedto, chloride, bromide, or iodide;

and mixtures thereof.

A first set of embodiments includes a composition comprising aninhibitor of nitrification; at least one polar solvent misciblecorrosion inhibitor; a first solvent, wherein said first solvent is apolar solvent which readily dissolves the nitrification inhibitor; andan optional second solvent, the optional second solvent is miscible inthe first solvent and wherein the second solvent is no more polar thanthe first solvent, in some of these embodiments the inhibitor ofnitrification is a (trichloromethyl) pyridine compound such asnitrapyrin (2-chloro-6-(trichloromethyl)pyridine.

A second set of embodiments is provided according to the first set ofembodiments wherein the at least one polar solvent miscible corrosioninhibitor is selected from the group consisting of:

(1) methylpyridines:

(2) pyridine carboxamides:

(e.g., nicotinamide and isomers thereof)

(3) pyridine carboxylic acid and esters:

(e.g., nicotinic acid, nicotinate esters, and isomers thereof)

(4) epoxidized seed or vegetable oils:

wherein R₁, R₂, and R₃ independently represent C₁₄-C₂₀ alkyl groupssubstituted with from zero to four epoxide groups.

(5) epoxy resin (based on bisphenol-type chemistry)

wherein R₁ and R₂ independently represent H, C₁-C₄ alkyl, or phenyl, andR₃ and R₄ independently represent H, C1-C4 alkyl, C1-C4 haloalkyl, orphenyl.

(6) 1,2-epoxyalkanes:

(e.g., 1,2-epoxydecane)

(7) 1-alkylimidazoles:

(8) amine salts of nicotinic acid:

wherein R¹, R² and R³ independently represent H, (C₁-C₁₈) alkyl or(C₁-C₁₈) alkyl substituted with one or more substituents selected from,but not limited to, halogen, hydroxy, alkoxy or alkylthio, provided thatthe substituents are sterically compatible and the rules of chemicalbonding and strain energy are satisfied, or any two of R1, R2 and R3represent —(CH2)n- where n is an integer from 3-5.

(9) primary, secondary & tertiary amines:

wherein R¹, R² and R³ independently represent H, (C₁-C₁₈) alkyl or(C₁-C₁₈) alkyl substituted with one or more substituents selected from,but not limited to, halogen, hydroxy, alkoxy or alkylthio, provided thatthe substituents are sterically compatible and the rules of chemicalbonding and strain energy are satisfied, or any two of R¹, R² and R³represent —(CH₂)_(n)— where n is an integer from 3-5.

(10) tertiary amine oxides:

wherein R⁴, R⁵ and R⁶ independently represent (C₁-C₁₈) alkyl or (C₁-C₁₈)alkyl substituted with one or more substituents selected from, but notlimited to, halogen, hydroxy, alkoxy or alkylthio, provided that thesubstituents are sterically compatible and the rules of chemical bondingand strain energy are satisfied, or any two of R¹, R² and R³ represent—(CH₂)_(n)— where n is an integer from 3-5, or

wherein R⁴ is a straight or branched chain (C₁-C₁₈) alkyl or analkyletherpropyl or alkylamidopropyl of the formula:

wherein R⁷ is a straight or branched chain (C₁₀-C₁₈) alkyl, and

R⁵ and R⁶ independently are straight or branched chain (C₁-C₁₈) alkyl orethoxylates or propoxylates of the formula:

wherein n is an integer from 1 to 20, or mixtures thereof.

(11) tetra-substituted ammonium salts:

wherein R¹, R² and R³ independently represents (C₁-C₁₆) alkyl or(C₁-C₁₈) alkyl substituted with one or more substituents selected from,but not limited to, halogen, hydroxy, alkoxy or alkylthio, provided thatthe substituents are sterically compatible and the rules of chemicalbonding and strain energy are satisfied, or any two of R¹, R² and R³represent —(CH₂)_(n)— where n is an integer from 3-5, R⁴ represents((C₁-C₁₆) alkyl or arylalkyl), and X⁻ is selected from, but not limitedto, chloride, bromide, or iodide. In some embodiments, N—((C₁₋C₁₆) alkylor arylalkyl) tri((C₁-C₁₆) alkyl)ammonium salts are those in which R¹,R², R³ and R⁴ are the same or where R¹, R² and R³ are CH₃ and R⁴ is(C₂-C₁₆) alkyl or arylalkyl.

A third set of embodiments includes a formulation, comprising:2-chloro-6-(trichloromethyl)pyridine, wherein the 2-chloro-6(trichloromethyl)pyridine is present in the formulation in the range ofabout 200 to about 400 g/L; at least one polar solvent, selected fromthe group consisting of: a mixture of N, N-dimethyloctanamide(N,N-dimethylcaprylamide) and N, N-dimethyldecanamide (N,N-dimethylcapramide); and a dibasic ester, wherein the first solventcomprises between about 40 to about 70 weight percent of theformulation; at least one polar solvent miscible corrosion inhibitor,selected from the group consisting of: a liquid epoxy resin; 2,6-dimethylpyridine; epoxidized linseed oil; and nicotinamide; whereineach said polar solvent miscible corrosion inhibitor, comprises about0.5 to about 2.5 weight percent; and at least one optional solventselected from the group consisting of: a solvent naphtha, wherein thesecond solvent comprises about 5.0 to about 20.0 weight percent of theformulation.

A fourth set of embodiments includes a formulation comprising: about 240to about 350 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 40 toabout 60 weight percent of a mixture of N, N-dimethyloctanamide (N,N-dimethylcaprylamide) and N, N-dimethyldecanamide (N,N-dimethylcapramide); about 0.5 to about 1.5 weight percent of liquidepoxy resin and about 0.5 to about 1.5 weight percent 2,6-dimethylpyridine; and about 5 to about 20 weight percent solventnaphtha.

A fifth set of embodiments includes a formulation comprising: about 230to about 300 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 45 toabout 55 weight percent of a mixture of N, N-dimethyloctanamide (N,N-dimethylcaprylamide) and N,N-dimethyldecanamide(N,N-dimethylcapramide); about 0.75 to about 1.4 weight percent ofliquid epoxy resin; about 0.5 to about 1.5 weight percent 2,6-dimethylpyridine; and about 10 to about 15 weight percent solventnaphtha.

A sixth set of embodiments includes a formulation comprising: about 240g/L of 2-chloro-6-(trichloromethyl)pyridine; about 50.0 to about 55weight percent of a mixture of N,N-dimethyloctanamide(N,N-dimethylcaprylamide) and N,N-dimethyldecanamide(N,N-dimethylcapramide); about 1.0 to about 1.1 weight percent of liquidepoxy resin oil; about 0.5 to about 1.5 weight percent 2,6-dimethylpyridine; and about 11.0 to about 14.0 weight percent solventnaphtha.

A seventh set of embodiments includes a formulation comprising: about240 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 50.55 weightpercent of a mixture of N, N-dimethyloctanamide (N,N-dimethylcaprylamide) and N, N-dimethyldecanamide(N,N-dimethylcapramide); about 1.2 weight percent of liquid epoxy resinoil; about 0.5 to about 1.5 weight percent 2, 6-dimethylpyridine; andabout 12.64 weight percent solvent naphtha.

An eighth set of embodiments includes a formulation comprising: about200 to about 400 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 20to about 50 weight percent of a dibasic ester; about 0.5 to about 2.5weight percent of epoxidized linseed oil; about 0.5 to about 2.5 weightpercent nicotinamide; and about 20.0 to about 50.0 weight percentcyclohexanone.

A ninth set of embodiments includes a formulation comprising: about 240g/L to about 350 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 45to about 55 weight percent of a dibasic ester; about 1.0 to about 2.0weight percent of epoxidized linseed oil; and about 0.8 weight percentnicotinamide; and about 11.0 to about 14.0 weight percent cyclohexanone.

A tenth set of embodiments includes a formulation comprising: about 240g/L of 2-chloro-6-(trichloromethyl)pyridine; about 50.47 weight percentof a dibasic ester; about 1.5 weight percent of epoxidized linseed oil;about 0.8 weight percent nicotinamide; and about 12.62 weight percentcyclohexanone.

A twelfth set of embodiments includes a formulation, comprising: about200 to about 400 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 40to about 60 weight percent of a dibasic ester; about 0.5 to about 2.5weight percent of epoxidized linseed oil; and about 0.4 to about 1.5weight percent nicotinamide.

A thirteenth set of embodiments include the twelfth embodiment: about240 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 63.08 weightpercent of a dibasic ester; about 1.5 weight percent of epoxidizedlinseed oil; and about 0.6 to about 1.0 weight percent nicotinamide.

A fourteenth set of embodiments include a formulation, comprising: about240 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 63.08 weightpercent of a dibasic ester; about 1.5 weight percent of epoxidizedlinseed oil; and about 0.8 weight percent nicotinamide.

A fifteenth set of embodiments includes a formulation, comprising: about200 to about 400 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 40to about 70 weight percent of triethyl phosphate; about 0.5 to about 2.5weight percent of epoxidized linseed oil; and about 0.5 to about 2.5weight percent of methyl nicotinate.

A sixteenth set of embodiments includes a formulation, comprising: about200 to about 400 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 40to about 70 weight percent of methoxybenzene; about 0.5 to about 2.5weight percent of nicotinamide; and about 0.5 to about 2.5 weightpercent of 2-amino-2-methyl-1-propanol.

A seventeenth set of embodiments including at least one of theformulations according to any of the first through the sixteenth set ofembodiments and at least additional agricultural ingredient selectedfrom the group consisting of: herbicides, insecticides, mitocides,fungicides, and fertilizers.

An eighteenth set of embodiments including any of the formulationsaccording to the seventeenth set of embodiments, wherein theagricultural ingredient is a fertilizer.

A nineteenth set of embodiments including any of the formulationaccording to the eighteenth set of embodiments, wherein the fertilizerincludes nitrogen.

A twentieth set of embodiments including methods for treating soil,comprising the steps of: applying at least one of the formulationsaccording to the first through the nineteenth set embodiments to atleast one area selected from the area consisting of: the surface of aportion of soil, beneath the surface of a portion of soil, a portion ofa plant, and a portion of a surface adjacent to a plant.

A twenty-first set of embodiments including any of the methods accordingto the twentieth set of embodiments, wherein the applying step includesinjecting at least one of the formulations into a portion of soil.

DETAILED DESCRIPTION

For the purposes of promoting an understanding of the principles of thenovel technology, reference will now be made to the preferredembodiments thereof, and specific language will be used to describe thesame. It will nevertheless be understood that no limitation of the scopeof the novel technology is thereby intended, such alterations,modifications, and further applications of the principles of the noveltechnology being contemplated as would normally occur to one skilled inthe art to which the novel technology relates are within the scope ofthis disclosure and the claims.

Unless noted otherwise as used herein the term ‘about’ refers to a rangeof values from less than 10 percent to greater than 10 percent of thestated value, for example about 1.0 encompasses values from 0.9 to 1.1.

(Trichloromethyl)pyridine compounds useful in the composition of thepresent invention include compounds having a pyridine ring which issubstituted with at least one trichloromethyl group and mineral acidsalts thereof. The presence of a (trichloromethyl)pyridine compoundsuppresses the nitrification of ammonium nitrogen in the soil or growthmedium, thereby preventing the rapid loss of ammonium nitrogenoriginating from nitrogen fertilizers, organic nitrogen constituents, ororganic fertilizers and the like. Suitable compounds include thosecontaining chlorine or methyl substituents on the pyridine ring inaddition to a trichloromethyl group, and are inclusive of chlorinationproducts of methyl pyridines such as the lutidines, the collidines andthe picolines. Suitable mineral acid salts of the(trichloromethyl)pyridine compounds include hydrochlorides, nitrates,sulfates and phosphates.

The (trichloromethyl)pyridine compounds useful in the practice of thepresent invention are typically oily liquids or crystalline solidsdissolved in a solvent. Other suitable compounds are described in U.S.Pat. No. 3,135,594. A preferred (trichloromethyl)pyridine is2-chloro-6-(trichloromethyl)pyridine, also known as nitrapyrin, and theactive ingredient of the product N-SERVE™ (Trademark of Dow AgroSciencesLLC).

N-SERVE™ has an active nitrapyrin loading level of about 240 g/L. Thenitrapyrin loading level of N-SERVE™ is set in part by the solubility ofnitrapyrin in the solvents used in the formulation (e.g., Aromatic 100)and its corrosiveness at elevated temperature (i.e., 50° C.). Stillother non-polar hydrophobic solvents which can be used in relativelynon-corrosive formulations of nitrapyrin include, but are not limitedto, other naphthalene depleted solvents, i.e., aromatic solvent thatincludes less than about 1% naphthalene. Some non-ionic, hydrophobicpost-added solvents that can be used to prepare liquid formulations ofnitrapyrin include, but are not limited to: cyclohexanone; Aromatic 100Fluid, also known as solvent naphtha or light aromatic; Aromatic 150Fluid, also known as solvent naphtha, heavy aromatic, high flasharomatic naphtha type II, heavy aromatic solvent naphtha, hydrocarbons,C10 aromatics, >1% naphthalene, A150, S150; and Aromatic 200 Fluid, alsoknown as solvent naphtha, heavy aromatic, high flash aromatic naphthatype II, heavy aromatic solvent naphtha, hydrocarbons, C10-13aromatics, >1% naphthalene, A200, and S200.

Nitrapyrin tends to be more soluble in polar solvents than in non-polarsolvents. Unfortunately, formulations of nitrapyrin in polar solventstend to be corrosive, especially towards carbon steel storagecontainers. Due at least in part to their corrosive properties,formulations of nitrapyrin in polar solvents have proved to be difficultto commercialize. Some aspects of the present invention includeidentifying and using especially useful corrosion inhibition additiveswhich make practical liquid formulations of nitrapyrin in polar solventthat include on the order of ˜360 g/L of nitrapyrin. These inventiveformulations are markedly less corrosive than are currently availablenitrapyrin polar solvent formulations.

In one embodiment, the (trichloromethyl)pyridine compound is nitrapyrin.The (trichloromethyl)pyridine compound is present in the liquidinhibitor composition at a lower range of 2% by weight of thecomposition, or in other embodiments, at a lower range of 3% by weightof the composition, or in other embodiments, at a lower range of 5% byweight of the composition.

In another embodiment, the (trichloromethyl)pyridine compound is presentin the liquid inhibitor composition at a lower range 0.5%, or 1%, or 2%,or 3%, or 4%, or 5%, 6%, or 8%, or 10% or 12% or 14%, by weight of thecomposition. In another embodiment, the (trichloromethyl)pyridinecompound is present in the liquid inhibitor composition at an upperrange of 75%, or 65%, or 60% by weight of the composition. In anotherembodiment, the (trichloromethyl)pyridine compound is present in theliquid inhibitor composition at an upper range of 60% by weight of thecomposition. In another embodiment, the (trichloromethyl)pyridinecompound is present in the liquid inhibitor composition at an upperrange of 55% by weight of the composition. In another embodiment, the(trichloromethyl)pyridine compound is present in the liquid inhibitorcomposition at an upper range of 59%, or 57%, or 55% or 53% or 50%, byweight of the composition. In another embodiment, the(trichloromethyl)pyridine compound is present in the liquid inhibitorcomposition at an upper range of 48%, or 46%, or 45% or 42% or 40%, byweight of the composition.

Described herein are high load compositions (in one embodiment, aloading level of 360 g/L) of nitrapyrin, which demonstrate stability invarious extreme conditions, such as cold conditions. The compositions asdescribed herein are also capable of provide corrosion resistance tocarbon steel tanks.

In one embodiment, the (trichloromethyl)pyridine compound is dispersedin the liquid inhibitor composition at loading level of at least 200g/L, or in another embodiment, at least 250 g/L, or in anotherembodiment, at least 300 g/L, or in another embodiment, at least 320g/L, or in a further embodiment, at least 340 g/L, or in anotherembodiment, at least 360 g/L, or in yet another embodiment, at least 380g/L, or in another embodiment, at least 400 g/L.

In one embodiment, the (trichloromethyl)pyridine compound, typically2-chloro-6-(trichloromethyl)pyridine, has a solubility at 25° C. of atleast 300 grams per liter (g/L), or in another embodiment, at least 320g/L, or in a further embodiment, at least 340 g/L, or in anotherembodiment, at least 360 g/L, or in yet another embodiment, at least 380g/L, or in another embodiment, at least 400 g/L.

In one embodiment, the liquid inhibitor composition are made bycontacting one or more nitrification inhibitors with a solventcomprising at least one organophosphate compound, whereby thenitrification inhibitor is dissolved or dispersed in the solvent. Theliquid inhibitor composition can further comprises at least oneadditional component, typically a corrosion inhibitor.

The liquid fertilizer compositions, as described herein, comprise: onemore nitrogenous fertilizer compounds; at least one nitrificationinhibitor comprising a (trichloromethyl)pyridine compound; a solventcomprising an organophosphate compound; and, optionally, a corrosioninhibitor. In one embodiment, the liquid inhibitor composition furthercomprises at least one additional component including, but not limitedto, a co-solvent, a pH adjustor, flow agents, preservatives, bufferingagents, antifoam agents, compatibility agents, deposition agents,dispersants, drift control agents, penetrants, surfactants, spreaders,and wetting agents, and the like.

In one embodiment, the nitrogenous fertilizer compound is anhydrousammonia.

In yet another aspect, described herein are liquid fertilizercompositions comprising, based on weight of the composition: (a) up toabout 99 wt %, by weight of composition, of one or more nitrogenousfertilizer compounds, which in one embodiment is anhydrous ammonia (b) a(trichloromethyl)pyridine compound, which in one embodiment is2-chloro-6-(trichloromethyl)pyridine, (c) a solvent comprising anorganophosphate compound, and (d) a corrosion inhibitor. In oneembodiment, the organophosphate compound is an alkyl phosphate. In oneembodiment, the organophosphate compound is triethyl phosphate. In oneembodiment, the organophosphate compound is triethyl phosphate,tri(isobutyl)phosphate, tributoxyethyl phosphate (TBEP) ortris(2-ethylhexyl) phosphate.

Methods of making a liquid fertilizer composition comprising contactingone or more nitrogenous fertilizer compounds with a liquid inhibitorcomposition, as described herein. In one embodiment, the nitrogenousfertilizer compound is anhydrous ammonia. The liquid inhibitorcomposition comprises, in one embodiment, at least one of anitrification inhibitor, which is dissolved or dispersed in a solventcomprising at least one organophosphate compound. In one embodiment, thenitrification inhibitor comprises a (trichloromethyl)pyridine compound.The liquid inhibitor composition, in one embodiment, further comprisesat least one additional component, typically a corrosion inhibitor.

In one embodiment, the liquid fertilizer compositions as describedherein are utilized for treating soil. The term “treating” in oneembodiment means contacting the compositions as described herein withsoil. The term “treating”, in yet another embodiment, means concurrentmechanical mixing of the described compositions with soil. In anotherembodiment, the term “treating” means applying the describedcompositions to the surface of the soil and thereafter mechanicallyincorporating the compositions into soil (for example, at a certaindepth). In yet another embodiment, the term “treating” meansincorporating the described compositions into the soil at a certaindepth, such as by injection and irrigation.

In one embodiment, the term “treating” means injecting the liquidfertilizer composition as described herein into soil at a depth of lessthan or equal to 10 inches. In another embodiment, the term “treating”means injecting the liquid fertilizer composition as described hereininto soil at a depth of less than or equal to 9 inches, or in someembodiments, less than or equal to 8 inches, or in some embodiments,less than or equal to 7 inches, or in some embodiments, less than orequal to 6 inches, or in some embodiments, less than or equal to 5inches, or in some embodiments, less than or equal to 4 inches, or insome embodiments, less than or equal to 3 inches.

In another aspect, described herein are methods for fertilizing targetplants, comprising applying a liquid fertilizer composition to soil orenvironment of a target plant, the liquid fertilizer compositioncomprising: one more nitrogenous fertilizer compounds; at least onenitrification inhibitor comprising a (trichloromethyl)pyridine compound;a solvent comprising an organophosphate compound, and, optionally, acorrosion inhibitor. In one embodiment, the liquid inhibitor compositionfurther comprises at least one additional component including, but notlimited to, a co-solvent, a pH adjustor, flow agents, preservatives,buffering agents, antifoam agents, compatibility agents, depositionagents, dispersants, drift control agents, penetrants, surfactants,spreaders, and wetting agents, and the like. In one embodiment, thenitrogenous fertilizer compound is anhydrous ammonia.

In one embodiment, the liquid inhibitor composition or liquid fertilizercomposition, as described herein, forms a stable composition attemperatures less than or equal to 15° C., or 10° C., or 7° C., or 5°C., or 3° C. In another embodiment, the liquid inhibitor composition orliquid fertilizer composition, as described herein, forms a stablecomposition at temperatures less than or equal to 0° C. In anotherembodiment, the liquid inhibitor composition or liquid fertilizercomposition, as described herein, forms a stable composition attemperatures less than or equal to −1° C., or −2° C., or −3° C., or −4°C., or −5° C., or −6° C., or −7° C., or −8° C., or −9° C., or −10° C. Inone embodiment, a stable composition means that no flocculation orcrystallization is observed over a period of time.

In one embodiment, the liquid inhibitor composition or liquid fertilizercomposition, as described herein, forms a stable composition for aperiod of at least 24 hours. In one embodiment, the liquid inhibitorcomposition or liquid fertilizer composition, as described herein, formsa stable composition for a period of at least 48 hours. In oneembodiment, the liquid inhibitor composition or liquid fertilizercomposition, as described herein, forms a stable composition for aperiod of at least 1 week. In one embodiment, the liquid inhibitorcomposition or liquid fertilizer composition, as described herein, formsa stable composition for a period of at least 2 weeks.

In one embodiment, the compositions as described herein are stable forat least 3 months in metal containers. In one embodiment, thecompositions as described herein are stable for at least 2 months inmetal containers at 25° C. (or in some embodiments, 50° C.). In oneembodiment, the compositions as described herein are stable for at least1 month in metal containers at 25° C. (or in some embodiments, 50° C.).The metal containers can be, in one embodiment, carbon steel containers.

In another embodiment, compounds suitable as the organic solventcomponent of the composition and methods of the present invention formliquid, or otherwise stable, compositions with the nitrificationinhibitor at temperatures at or greater than −16° C., in alternativeembodiments, greater than −14° C., in other embodiments, greater than−12° C., in other embodiments, greater than −10° C., in furtherembodiments, greater than −8° C., in other embodiments, greater than −5°C., in other embodiments, greater than −3° C., in other embodiments,greater than −2° C., in other embodiments, greater than 0° C., in otherembodiments, greater than 2° C., in other embodiments, greater than 4°C., in other embodiments, greater than 5° C.

In some embodiments, at the specified temperature ranges or at greaterthan a specified temperature (as described herein), the liquidfertilizer composition is stable, meaning the nitrification inhibitor(s)do not react with the solvent or solvent component under anticipatedmanufacturing, storage, and use conditions. In another embodiment, atthe specified temperature ranges or at greater than a specifiedtemperature (as described herein), the liquid fertilizer composition isstable, meaning the liquid fertilizer composition or liquid inhibitorcomposition is or substantially is in one phase, i.e., no visiblecrystals, no visible precipitation, and/or no visible multiple liquidphases.

In one embodiment, the organophosphate compound is according to formula(I)

wherein R1, R2 and R3, are each independently chosen from H, a C1-C16alkyl group, a C1-C16 alkenyl, group, a C1-C16 alkoxyalkyl group, aC7-C30 alkylarylalkyl group, a C7-C30 arylalkyl group, or an aryl group;provided that at least one of R1, R2 or R3 is not H. In anotherembodiment, R1, R2 and R3, are each independently chosen from H, aC1-C12 alkyl group, a C1-C12 alkenyl, group, a C1-C12 alkoxyalkyl group,a C7-C30 alkylarylalkyl group, a C7-C30 arylalkyl group, or an arylgroup; provided that at least one of R1, R2 or R3 is not H. In oneembodiment, R1, R2 and R3, are each independently chosen from H, a C1-C4alkyl group, a C4-C8 alkyl group, a C1-C12 alkenyl, group, a C1-C4alkoxyalkyl group, a C7-C30 alkylarylalkyl group, a C7-C30 arylalkylgroup, or an aryl group; provided that at least one of R1, R2 or R3 isnot H.

In yet another embodiment, R1, R2 and R3, are each independently chosenfrom a linear or branched C1-C12 alkyl group, a linear or branchedC1-C12 alkenyl, group, a linear or branched C1-C12 alkoxyalkyl group, alinear or branched C7-C30 alkylarylalkyl group, a linear or branchedC7-C30 arylalkyl group, or an aryl group. In one embodiment, R1, R2 andR3, are each independently chosen from a C1-C12 alkyl group, moretypically, a C2-C8 alkyl group.

In one embodiment, R1, R2 and R3, are each independently a C1-C3 alkylgroup, typically an ethyl group. In another embodiment, R1, R2 and R3,are each independently a branched C1-C12 alkyl group, typically, a2-ethylhexyl group. In one embodiment, R1, R2 and R3, are eachindependently a C1-C12 alkoxyalkyl group, typically a butoxyethyl group.

The present invention described herein will become apparent from thefollowing detailed description and examples, which comprises in oneaspect, a liquid inhibitor composition for use in agriculturalapplications and/or liquid fertilizer compositions comprising: at leastone nitrification inhibitor comprising a (trichloromethyl)pyridinecompound; a polar solvent blend comprising at least two polar solvents:(i) a dibasic ester blend and (ii) a ketone such as cyclohexanone; and,optionally, a corrosion inhibitor.

In another aspect, described herein are methods of making liquidinhibitor compositions comprising contacting one or more nitrificationinhibitors with a polar solvent blend comprising at least two polarsolvents: (i) a dibasic ester blend and (ii) a ketone such ascyclohexanone, whereby the nitrification inhibitor is dissolved ordispersed in the polar solvent blend. In one embodiment, thenitrification inhibitor comprises a (trichloromethyl)pyridine compound.The liquid inhibitor composition, in one embodiment, further comprisesat least one additional component, typically a corrosion inhibitor.

In another aspect, described herein are liquid fertilizer compositionsfor use in agricultural applications comprising: one or more nitrogenousfertilizer compounds; at least one nitrification inhibitor comprising a(trichloromethyl)pyridine compound; a polar solvent blend comprising atleast two polar solvents: (i) a dibasic ester blend and (ii) a ketonesuch as cyclohexanone; and, optionally, a corrosion inhibitor.

In certain embodiments, the dibasic ester blend comprises:

a diester of formula (IIa):

a diester of formula (IIb):

and

a diester of formula (IIc):

R₁ and/or R₂ can individually comprise a hydrocarbon having from about 1to about 8 carbon atoms, typically, methyl, ethyl, propyl, isopropyl,butyl, isobutyl, n-butyl, isoamyl, hexyl, heptyl or octyl.

In certain other embodiments, the dibasic ester blend comprises:

a diester of the formula (IIIa):

a diester of the formula (IIIb):

and, optionally,

a diester of the formula (IIIc):

R₁ and/or R₂ can individually comprise a hydrocarbon having from about 1to about 8 carbon atoms, typically, methyl, ethyl, propyl, isopropyl,butyl, isobutyl, n-butyl, isoamyl, hexyl, heptyl, or octyl. In suchembodiments, the blend typically comprises (by weight of the blend) (i)from about 5% to about 30% of the diester of formula (IIIc), (ii) fromabout 70% to about 95% of the diester of formula (IIIb), and (iii) fromabout 0% to about 10% of the diester of formula (IIIc). More typically,the blend typically comprises (by weight of the blend): (i) from about6% to about 12% of the diester of formula (IIIa), (ii) from about 86% toabout 92% of the diester of formula (IIIb), and (iii) from about 0.5% toabout 4% of the diester of formula (IIIc).

Most typically, the blend comprises (by weight of the blend): (i) about9% of the diester of formula (IIIa), (ii) about 89% of the diester offormula (IIIb), and (iii) about 1% of the diester of formula (Inc). Theblend is generally characterized by a flash point of 98° C., a vaporpressure at 20° C. of less than about 10 Pa, and a distillationtemperature range of about 200-275° C.

In some embodiments, the polar solvent blend comprises (by weight of thesolvent blend) up to 100 wt % or 99.9 wt % of the ketone. In oneembodiment, the polar solvent blend comprises (by total weight of thepolar solvent blend) up to 80 wt % of the ketone. In one embodiment, thepolar solvent blend comprises (by total weight of the polar solventblend) up to 90 wt % of the ketone. In one embodiment, the polar solventblend comprises (by total weight of the polar solvent blend) up to 70 wt% of the ketone. In one embodiment, the polar solvent blend comprises(by total weight of the polar solvent blend) up to 65 wt % of theketone. In one embodiment, the polar solvent blend comprises (by totalweight of the polar solvent blend) up to 60 wt % of the ketone. In oneembodiment, the polar solvent blend comprises (by total weight of thepolar solvent blend) up to 55 wt % of the ketone. In one embodiment, thepolar solvent blend comprises (by total weight of the polar solventblend) up to 50 wt % of the ketone. In one embodiment, the polar solventblend comprises (by total weight of the polar solvent blend) up to 45 wt% of the ketone. In one embodiment, the polar solvent blend comprises(by total weight of the polar solvent blend) up to 40 wt % of theketone. It is believe that the composition of the polar solvent blendallows for the loading levels as described herein.

Suitable example of ketones include but are not limited to any one ormore of acetone, methyl ethyl ketone, methyl propyl ketone,cyanoacetone, ethoxy: acetone, acetonylacetone, diacetone alcohol,methyl isobutyl ketone, diethyl ketone, diisopropyl ketone, diisobutylketone, methyl-n-amyl ketone, methyl-n-hexyl ketone, cyclopentanone,methylcyclohexanone, methyl-cyclopentanone, cyclohexanone,methylallylcyclohexanone, phenylcyclohexanone, cyclohexylcyclohexanone,benzylcyclohexanone, phorone, isophorone, and, B-ionone, methyl vinylketone, methyl isopropenyl ketone, methyl propenyl ketone, mesityloxide, chloroacetone, acetophenone, benzophenone, methyl 2-naphthylketone, propiophenone, butyrophenone, p-acetyl biphenyl,p-methylacetophenone, p-methoxyacetophenone, p-chloroacetophenone,p-bromoacetophenone, acetoa'cetic ester, acetoacetic nitrile,acetoacetic amide, acetyl-p cymene, dibenzyl ketone, and the like. Inone embodiment, the ketone is cyclohexanone.

In some embodiments, the dibasic ester blend comprises adducts ofalcohol and linear diacids, each adduct having the formula (IV):

R—OOC-A-COO—R  (IV)

wherein R is an alkyl group (e.g., methyl, ethyl, etc.) and A is amixture of —(CH2)4-, —(CH2)3, and —(CH2)2-. In other embodiments, theblend comprises adducts of alcohol, typically ethanol, and lineardiacids, the adducts having the formula R1-OOC-A-COO—R2, wherein atleast part of R1 and/or R2 are residues of at least one linear alcoholhaving 4 carbon atoms, and/or at least one linear or branched alcoholhaving at least 5 carbon atoms, and wherein A is a divalent linearhydrocarbon. In some embodiments A is one or a mixture of —(CH2)4-,—(CH2)3, and —(CH2)2-. In other embodiments, the dibasic ester comprisesadducts of an alcohol and linear or branched diacids, the adducts havingthe formula (IV): R—OOC-A-COO—R, wherein R is an alkyl group (e.g.,methyl, ethyl, etc.) and A one of the following: —(CH2)4-, —(CH2)3,—(CH2)2-, —CH2-, or any mixture thereof.

The dibasic ester blend may be derived from one or more by-products inthe production of polyamide, for example, polyamide 6,6. In oneembodiment, at least one dibasic ester comprises a blend of linear orbranched, cyclic or noncyclic, C1-C20 alkyl, aryl, alkylaryl orarylalkyl esters of adipic diacids, glutaric diacids, and succinicdiacids. In another embodiment, the composition comprises a blend oflinear or branched, cyclic or noncyclic, C1-C20 alkyl, aryl, alkylarylor arylalkyl esters of adipic diacids, methylglutaric diacids, andethylsuccinic diacids

Generally, polyamide is a copolymer prepared by a condensation reactionformed by reacting a diamine and a dicarboxylic acid. Specifically,polyamide 6,6 is a copolymer prepared by a condensation reaction formedby reacting a diamine, typically hexamethylenediamine, with adicarboxylic acid, typically adipic acid.

In one embodiment, the blend of dibasic esters can be derived from oneor more by-products in the reaction, synthesis and/or production ofadipic acid utilized in the production of polyamide, the compositioncomprising a blend of dialkyl esters of adipic diacids, glutaricdiacids, and succinic diacids (herein referred to sometimes as “AGS” orthe “AGS blend”), In one embodiment the dibasic ester blend comprisesdimethyl adipate, dimethyl glutarate and dimethyl succinate.

In one embodiment, the blend of esters is derived from by-products inthe reaction, synthesis and/or production of hexamethylenediamineutilized in the production of polyamide, typically polyamide 6,6. Thecomposition comprises a blend of dialkyl esters of methylglutaricdiacids, ethylsuccinic diacids, and optionally adipic diacids (hereinreferred to sometimes as “MGA”, “MGN”, “MGN blend” or “MGA blend”). Inone embodiment the dibasic ester blend comprises dimethyl adipate,dimethyl methylglutarate and dimethyl ethylsuccinate.

In one embodiment, the liquid inhibitor composition or liquid fertilizercomposition further comprises at least one additional componentincluding, but not limited to, a co-solvent, a pH adjustor, flow agents,preservatives, buffering agents, antifoam agents, compatibility agents,deposition agents, dispersants, drift control agents, penetrants,surfactants, spreaders, and wetting agents, and the like. In oneembodiment, the nitrogenous fertilizer compound is anhydrous ammonia.

In another aspect, described herein are methods of making a liquidfertilizer compositions comprising contacting one or more nitrogenousfertilizer compounds with liquid inhibitor composition. In oneembodiment, the nitrogenous fertilizer compound is anhydrous ammonia.The liquid inhibitor composition comprises, in one embodiment, at leastone of a nitrification inhibitor, which is dissolved or dispersed in asolvent blend comprising at least two polar solvents: (i) a dibasicester blend and (ii) a ketone such as cyclohexanone. In one embodiment,the nitrification inhibitor comprises a (trichloromethyl)pyridinecompound. The liquid inhibitor composition, in one embodiment, furthercomprises at least one additional component, typically a corrosioninhibitor.

In another embodiment, one or more second solvents can be used todissolve or disperse (trichloromethyl)pyridine compounds at high loadinglevels and include, but are not limited to, solvent naphtha, aromaticsolvents, mineral oils, kerosene, and chlorinated aliphatic and aromatichydrocarbons. In one particular embodiment, the one or more secondsolvents used to dissolve or disperse (trichloromethyl)pyridinecompounds at high loading levels include but are not limited to xyleneand solvent naphtha.

In one particular embodiment, the co-solvent is an esteramide compoundaccording to formula (II):

R1OOC-A-CONR2R3  (II)

wherein:

-   -   A is a divalent linear or branched (C2-C8)aliphatic group, and        R1, R2, and R3 are each independently (C1-C12)alkyl,        (C1-C12)aryl, (C1-C12)alkaryl or (C1-C12)arylalkyl, and R2 and        R3 may each optionally be substituted with one or more hydroxyl        groups.

The inventive formulations of (trichloromethyl)pyridine compound may beapplied to the soil or a growth medium at a rate in the range of atleast one lower limit selected from the group of lower limits consistingof about 0.1, about 0.25, about 0.5 and about 0.58 kg/hectare to atleast one upper limit selected from the group consisting of about 1.0,about 1.2 and about 1.5 kg/hectare. The preferred amount can be easilyascertained by the application preference, considering factors such assoil pH, temperature, soil type and mode of application.

The formulations of the present invention can be applied in any mannerwhich will benefit the crop of interest. In one embodiment the inventiveformulation is applied to growth medium in a band or row application. Inanother embodiment, the formulation is applied to or throughout thegrowth medium prior to seeding or transplanting the desired crop plant.In yet another embodiment, the formulation can be applied to the rootzone of growing plants.

The soil may be prepared in any convenient manner compatible with theuse of the present invention, including mechanically mixing theformulation with the soil. Still other application may include applyingthe formulation to the surface of the soil and thereafter dragging,dicing or cutting the formulation into the soil to a desired depth.Still other methods of delivering the nitrification inhibitor into thesoil, include methods such as injection, and spraying, or irrigation. Inmany applications the (trichloromethyl)pyridine compound is deliveredinto the soil to the desired depth of up to 6 inches (15.24 cm.).

In some embodiments the inventive nitrapyrin formulation may be usedalong with other agriculturally active ingredients such as insecticides,fungicides, mitocides, herbicides, and the like.

Some exemplary herbicides which can be used along with the inventivenitrapyrin formulations include, but are not limited to acetochlor,alachlor, aminopyralid, atrazine, benoxacor, bromoxynil, carfentrazone,chlorsulfuron, clodinafop, clopyralid, dicamba, diclofop-methyl,dimethenamid, fenoxaprop, flucarbazone, flufenacet, flumetsulam,flumiclorac, fluroxypyr, glufosinate-ammonium, glyphosate,halosulfuron-methyl, imazamethabenz, imazamox, imazapyr, imazaquin,imazethapyr, isoxaflutole, quinclorac, MCPA, MCP amine, MCP ester,mefenoxam, mesotrione, metolachlor, s-metolachlor, metribuzin,metsulfuron methyl, nicosulfuron, paraquat, pendimethalin, picloram,primisulfuron, propoxycarbazone, prosulfuron, pyraflufen ethyl,rimsulfuron, simazine, sulfosulfuron, thifensulfuron, topramezone,tralkoxydim, triallate, triasulfuron, tribenuron, triclopyr,trifluralin, 2,4-D, 2,4-D amine, 2,4-D ester and the like, 4-CPA, 4-CPB,4-CPP, 2,4-D, 3,4-DA, 2,4-DB, 3,4-DB, 2,4-DEB, 2,4-DEP, 3,4-DP,2,4,5-TB, 2,3,6-TBA, allidochlor, acetochlor, acifluorfen, aclonifen,alachlor, alloxydim, alorac, ametridione, ametryn, amibuzin,amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid,aminopyralid, amiprofos-methyl, amitrole, anilofos, anisuron, asulam,asulam, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne,barban, BCPC, beflubutamid, benazolin, bencarbazone, benfluralin,benfuresate, bensulfuron, bensulide, bentazone, benzadox, benzfendizone,benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop,benzthiazuron, bicylopyrone, bifenox, bilanafos, bilanafos, bispyribac,bromacil, bromobonil, bromobutide, bromofenoxim, bromoxynil,brompyrazon, butachlor, butafenacil, butamifos, butenachlor,buthidazole, buthiuron, butralin, butroxydim, buturon, butylate,cafenstrole, cafenstrole, cambendichlor, carbasulam, carbasulam,carbetamide, carboxazole chlorprocarb, carfentrazone, CDEA, CEPC,chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine,chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop,chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen,chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham,chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin,cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop, clofop,clomazone, clomeprop, clomeprop, cloprop, cloproxydim, clopyralid,clopyralid, cloransulam, CPMF, CPPC, credazine, cumyluron, cyanatryn,cyanazine, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop,cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon, dazomet,delachlor, desmedipham, desmetryn, diallate, dicamba, dichlobenil,dichloralurea, dichlormate, dichlorprop, dichlorprop-P, diclofop,diclosulam, diethamquat, diethatyl, difenopenten, difenoxuron,difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate,dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimexano,dimidazon, dinitramine, dinitramine, dinofenate, dinoprop, dinosam,dinoseb, dinoterb, diphenamid, dipropetryn, diquat, disul, dithiopyr,diuron, DMPA, DNOC, EBEP, eglinazine, endothal, epronaz, epronaz, EPTC,erbon, esprocarb, ethalfluralin, ethametsulfuron, ethidimuron,ethiolate, ethofumesate, ethoxyfen, ethoxysulfuron, etinofen,etnipromid, etnipromid, etnipromid, etobenzanid, EXD, fenasulam,fenasulam, fenasulam, fenoprop, fenoxaprop, fenoxaprop-P, fenoxasulfone,fenteracol, fenthiaprop, fentrazamide, fenuron, flamprop, flamprop-M,flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazolate,flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican,flufenpyr, flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropyn,fluometuron, fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen,fluothiuron, flupoxam, flupoxam, flupropacil, flupropanate,flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone,fluthiacet, fomesafen, fomesafen, foramsulfuron, fosamine, furyloxyfen,glufosinate, glyphosate, halauxifen, halosafen, halosafen, halosulfuron,haloxydine, haloxyfop, haloxyfop-P, hexazinone, imazamethabenz,imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron,indanofan, indaziflam, iodobonil, iodosulfuron, ioxynil, ipazine,ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin,isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben,isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox,lactofen, lenacil, linuron, MCPA, MCPA-thioethyl, MCPB, mecoprop,mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine,mesosulfuron, mesotrione, metam, metamifop, metamifop, metamitron,metazachlor, metazosulfuron, metflurazon, methabenzthiazuron,methalpropalin, methazole, methiobencarb, methiozolin, methiuron,methiuron, methometon, methoprotryne, methyldymron, metobenzuron,metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron,metribuzin, metsulfuron, molinate, monalide, monisouron,monochloroacetic acid, monolinuron, monuron, morfamquat, naproanilide,napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, nitralin,nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb,orthosulfamuron, oryzalin, oryzalin, oxadiargyl, oxadiazon, oxapyrazon,oxasulfuron, oxaziclomefone, oxyfluorfen, parafluron, paraquat,pebulate, pelargonic acid, pendimethalin, penoxsulam, pentanochlor,pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham,phenmedipham-ethyl, phenobenzuron, picloram, picloram, picolinafen,picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron,procyazine, prodiamine, prodiamine, profluazol, profluralin, profoxydim,proglinazine, prometon, prometryn, propachlor, propanil, propaquizafop,propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron,propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, prynachlor,pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazolynate,pyrazosulfuron, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor,pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac,pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine,quinonamid, quizalofop, quizalofop-P, rhodethanil, rimsulfuron,sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton,simetryn, sulcotrione, sulfallate, sulfentrazone, sulfometuron,sulfosulfuron, sulglycapin, swep, tebutam, tebuthiuron, tefuryltrione,tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton,terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron,thiazopyr and triclopyr, thidiazimin, thidiazuron, thidiazuron,thiencarbazone-methyl, thifensulfuron, thiobencarb, tiocarbazil,tioclorim, topramezone, tralkoxydim, tri-allate, triasulfuron,triaziflam, tribenuron, tricamba, tridiphane, trietazine,trifloxysulfuron, trifluralin, triflusulfuron, trifop, trifopsime,trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron,vernolate, xylachlor, and compounds of the following Formula

wherein Ar represents a phenyl group substituted with one to foursubstituents independently selected from halogen, C1-C6 alkyl, C1-C6alkoxy, C2-C4 alkoxyalkyl, C2-C6 alkylcarbonyl, C1-C6 alkylthio, C1-C6haloalkyl, C1-C6 haloalkoxy, C2-C4 haloalkoxyalkyl, C2-C6haloalkylcarbonyl, C1-C6 haloalkylthio, —OCH2CH2-, —OCH2CH2CH2-, —OCH2O—or —OCH2CH2O—; R represents H or F; X represents C1 or vinyl; and Yrepresents C1, vinyl or methoxy; and their salts and esters asdisclosed, for example, in U.S. Pat. No. 7,314,849 B2, U.S. Pat. No.7,300,907 B2, U.S. Pat. No. 7,786,044 B2 and U.S. Pat. No. 7,642,220 B2.Depending upon the stability of the herbicide compounds used in thepresence of the component of the inventive formulation and the preferredmode of applying the compounds these compounds may be applied along withthe inventive nitrapyrin formulation. In many instances the compound maybe applied by any suitable means either before or after the inventiveformulation is applied to the soil.

Especially suitable herbicides useful with the compositions and methodsdescribed herein include 2,4-D, 2,4-DB, aminocyclopyrachlor,aminopyralid, clopyralid, dicamba, fluroxypyr, halauxifen, MCPA, MCPB,picloram, triclopyr, acetochlor, atrazine, benfluralin, cloransulam,cyhalofop, diclosulam, dithiopyr, ethalfluralin, florasulam,flumetsulam, glufosinate, glyphosate, haloxyfop, isoxaben, MSMA,oryzalin, oxyfluorfen, pendimethalin, penoxsulam, propanil, pyroxsulam,quizalofop, tebuthiuron, trifluralin, and the compound of the Formula.

and its C1-C12 alkyl or C7-C12 arylalkyl ester or salt derivatives suchas, for example, the benzyl ester.

Some exemplary insecticides which can be used along with the inventivenitrapyrin formulations include, but are not limited to abamectin,acephate, acetamiprid, acrinathrin, alpha-cypermethrin,alpha-endosulfan, azadirachtin, azinphos-ethyl, azinphos-methyl,bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin,bifenthrin, bufencarb, buprofezin, butacarb, cadusafos, carbaryl,carbofuran, carbosulfan, cartap, cartap hydrochloride,chlorantraniliprole, chlorfenapyr, chlorfenvinphos, chlorfluazuron,chlormephos, chlorpyrifos, chlorpyrifos-methyl, chromafenozide,clothianidin, cyantraniliprole, cyfluthrin, cyhalothrin, cypermethrin,deltamethrin, diazinon, dicrotophos, diflubenzuron, dimethoatedinotefuran, disulfoton, emamectin, emamectin benzoate, endosulfan,endothion, endrin, EPN, esfenvalerate, etaphos, ethiofencarb, ethion,ethiprole, ethoate-methyl, etofenprox, fenamiphos, fenazaflor,fenethacarb, fenitrothion, fenobucarb, fenpropathrin, fensulfothion,fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid,flubendiamide, flucythrinate, fonofos, fufenozide, furathiocarb,gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, heptenophos,hyquincarb, imidacloprid, indoxacarb, isazofos, isobenzan, isocarbophos,isofenphos, isofenphos-methyl, isoprocarb, isothioate, isoxathion,kinoprene, lambda-cyhalothrin, lepimectin, lufenuron, malathion,methamidophos, methomyl, methoxyfenozide, mevinphos, mexacarbate,milbemectin, monocrotophos, nitenpyram, novaluron, omethoate, oxamyl,oxydemeton-methyl, oxydeprofos, oxydisulfoton, parathion,parathion-methyl, penfluron, permethrin, phenthoate, phorate, phosalone,phosfolan, phosmet, phosphamidon, pirimetaphos, pirimicarb,pirimiphos-ethyl, pirimiphos-methyl, primidophos, profenofos,profluthrin, promecarb, propaphos, propoxur, prothiofos, pymetrozine,pyrafluprole, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen,spinetoram, spinosad, spirotetramat, sulfoxaflor, sulprofos,tau-fluvalinate, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin,tetramethylfluthrin, theta-cypermethrin, thiacloprid, thiamethoxam,thicrofos, thiocyclam, thiocyclam oxalate, thiodicarb, thiometon,thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin,tolfenpyrad, triazophos, triflumuron and zeta-cypermethrin. Dependingupon the stability of the insecticide compounds used in the presence ofthe component of the inventive formulation and the preferred mode ofapplying the compounds these compounds may be applied along with theinventive nitrapyrin formulation. In many instances the compound may beapplied by any suitable means either before or after the inventiveformulation is applied to the soil.

Some exemplary fungicides which can be used along with the inventivenitrapyrin formulations include, but are not limited to tricyclazole,phthalide, carpropamide, pyroquilon, diclocymet, fenoxanil, probenazole,isoprothiolane, iprobenfos, isotianil, tiadinil, kasugamycin,flutolanil, mepronil, pencycuron, polyoxins, validamycin,toclophos-methyl, boscalid, penthiopyrad, thifluzamide, bixafen,fluopyram, isopyrazam, propiconazole, difenoconazole, fenbuconazole,ipconazole, triadimefon, hexaconazole, azoxystrobin, metaminostrobin,orysastrobin and acibenzolar-S-methyl. Some of these fungicides may notbe effective for disease control when applied at the timing ofapplication of the inventive formulation because fungal diseasepropagation and growth cycles may not be optimal. The effective use andapplication timing of these fungicides can be easily determined by oneof normal skill in the art. Depending upon the stability of thefungicide compounds used in the presence of the component of theinventive formulation and the preferred mode of applying the compoundsthese compounds may be applied along with the inventive nitrapyrinformulation. In many instances the compound may be applied by anysuitable means either before or after the inventive formulation isapplied to the soil.

Some exemplary herbicide safeners which can be used along with theinventive nitrapyrin formulations include, but are not limited tobenoxacor, benthiocarb, cloquintocet-mexyl, daimuron, dichlormid,dicyclonon, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole,fluxofenim, furilazole, Harpin proteins, isoxadifen-ethyl,mefenpyr-diethyl, mephenate, MG 191, MON 4660, naphthalic anhydride(NA), oxabetrinil, 829148 and N-phenyl-sulfonylbenzoic acid amides.Depending upon the stability of the herbicide safener compounds used inthe presence of the component of the inventive formulation and thepreferred mode of applying the compounds these compounds may be appliedalong with the inventive nitrapyrin formulation. In many instances thecompound may be applied by any suitable means either before or after theinventive formulation is applied to the soil.

Some exemplary plant growth regulators which can be used along with theinventive nitrapyrin formulations include, but are not limited to 2,4-D,2,4-DB, IAA, IBA, naphthaleneacetamide, α-naphthaleneacetic acid,kinetin, zeatin, ethephon, aviglycine, 1-methylcyclopropene (1-MCP),ethephon, gibberellins, gibberellic acid, abscisic acid, ancymidol,flurprimidol, mefluidide, paclobutrazol, tetcyclacis, uniconazole,brassinolide, brassinolide-ethyl and ethylene. Depending upon thestability of the plant growth regulator compounds used in the presenceof the component of the inventive formulation and the preferred mode ofapplying the compounds these compounds may be applied along with theinventive nitrapyrin formulation. In many instances the compound may beapplied by any suitable means either before or after the inventiveformulation is applied to the soil.

Exemplary Formulations

The high load nitrapyrin SL formulations (360 g/L) comprising polarsolvents were prepared by dissolving nitrapyrin technical in the solventsystems, which included polar solvent miscible corrosion inhibitors. Thesolutions were mixed under IKA mixing until they were essentiallyhomogeneous.

Referring now to Table 1. All samples were tested for metal corrosionstability at different time intervals at 50° C. temperature and comparedagainst N-Serve commercial control formulation. Results are shown in theTable 1. Metal coupons (Carbon steel; AISI 1018) were tested forcorrosion stability in 40 ml prepared nitrapyrin formulations. Couponswere ˜45% submerged in the solution for the corrosion testing. Metalcoupons were approximately one half inch in width and three inches inlength with a thickness of 1/16th to ⅛th of an inch. During the testing,coupons were visually inspected for corrosion by checking any colorchanges or residue deposits on the coupon surface. The results of theseexperiments are summarized in Table 1.

TABLE 1 Example composition of stable high load nitrapyrin SLformulations (360 g/L nitrapyrin technical) comprising polar solventsafter corrosion testing with carbon steel coupons at 50° C. Control(N-Serve) sample has a nitrapyrin loading of 240 g/L. Nitrapyrin # ofdays technical Corrosion without Sample Loading Inhibitor visible # (Wt%) Solvents Additives corrosion 1 24.74 Aromatic 100 ELO 53 (Control)(66.53 wt (0.75 wt %) %)Xylene (7.398 wt %) 2 34.6 Hallcomid ELO 67M-8-10 (1 wt %)2,6 (63.4 wt %) Lutidine (1 wt %) 3 34.6 Hallcomid ELO (17 M-8-10 wt %)Nicotin- (63.4 wt %) amide (1 wt %) 4 32.9 CyclohexanoneDER331 53 (6439 wt %) (1.2 wt %)2,6 Lutidine (1 wt %) 5 34.6 HallcomidDER331 43 M-8-10 (1.2 wt %)2,6 (63.2 wt %) Lutidine (1 wt %) 6 32.94Cyclohexanone DER331 46 (51.89 wt %)Aro- (1.2 wt %)2,6 matic 100Lutidine (12.97 wt %) (1 wt %) 7 34.62 Hallcomid ELO 67 M-8-10 (1 wt%)2,6 (50.71 wt %)Aro- Lutidine matic 100 (1 wt %) (12.68 wt %) 8 34.62Hallcomid DER331 >120 M-8-10 (1.2 wt %)2,6 (50.55 wt %)Aro- Lutidinematic 100 (1 wt %) (12.64 wt %) 9 32.94 Cyclohexanone DER331 (1.8 32(51.41 wt %)Aro- wt %)α- matic 100 picoline (12.85 wt %) (1 wt %) 1034.62 Hallcomid ELO (1.5 22 M-8-10 wt %)Nicotin- (50.71 wt %)Aro- amidematic 100 (0.5 wt %) (12.68 wt %) 11 34.62 Hallcomid ELO (1.5 51 M-8-10wt %)Nicotin- (50.71 wt %)Aro- amide matic 100 (2.5 wt %) (12.68 wt %)12 34.62 Hallcomid DER331 (1.2 35 M-8-10 wt %)α- (50.55 wt %)Aro-picoline matic 100 (1 wt %) (12.64 wt %) 13 34.29 Hallcomid DER331 (1.818 M-8-10 wt %)Nicotin- (46.44 wt %)Aro- amide matic 100 (2 wt %) (15.48wt %) 14 34.29 Hallcomid ELO (1.5 30 M-8-10 wt %)Nicotin- (61.89 wt %)amide (2 wt %) 15 34.62 RhodiaSolv ELO (1.5 >120 RPDE wt %)Nicotin-(50.47 wt %)Cyclo- amide hexanone (.8 wt %) (12.62 wt %) 16 34.62RhodiaSolv ELO (1.5 105 RPDE wt %)Nicotin- (63.08 wt %) amide (0.8 wt %)17 34.62 RhodiaSolv ELO 19 RPDE (1.5 wt %) (63.88 wt %) 18 30.90RhodiaSolv ELO (1 4 PolarClean wt %)Nicotin- (67.10 wt %) amide (1 wt %)19 30.90 RhodiaSolv ELO 4 PolarClean (1 wt %)2,6 (67.10 wt %) Lutidine(1 wt %) 20 30.90 RhodiaSolv DER331 4 RPDE (1.2 wt %) (66.90 wt %) 2,6Lutidine (1 wt %) 21 30.90 RhodiaSolv DER331 4 RPDE (1.2 wt %) (66.90 wt%) Nicotinamide (1 wt %) 22 32.94 Dowanol DPM DER331 3 (62.76 wt %) (1.8wt %) Nicotinamide (2.5 wt %) 23 33.65 Dowanol DPM ELO 3 (62.35 wt %)(1.5 wt %) Nicotinamide (2.5 wt %) 24 34.6 TamiSolve NxG ELO 4 (61.40 wt%) (1.5 wt %) Nicotinamide (2.5 wt %)Common chemical names of commercially available solvents found in Table1: Hallcomid M-8-10: Mixture of N,N-dimethyloctanamide(N,N-dimethylcaprylamide) and N,N-dimethyldecanamide(N,N-dimethylcapramide); RhodiaSolv RPDE: Solvent mixture composed of areaction mass of dimethyl adipate, dimethyl glutarate and dimethylsuccinate; and Aromatic 100: Solvent Naphtha (petroleum), lightaromatic; TamiSolve NxG: N-butylpyrrolidone.

Example 2

A stock solution of 360 g/L nitrapyrin technical grade in triethylphosphate was prepared and additives in specific amounts to limitcorrosion to carbon steel were added to this solution. A small quantity(˜15 mL) of the solution in glass jars were left for storage stabilityat room temperature (˜20 C) and −12 C. The −12 C sample was seeded afterit reached 24 hrs age by incorporating few small grains of nitrapyrintechnical in the cold solution and was immediately stored back to the−12 C storage temperature. A carbon steel coupon was partially submergedinto the solution stored at 54 C. The coupon was periodically observedfor any sign of corrosion in liquid and vapor phases. The solutions atroom temperature and −12 C were observed for any inhomogeneity,crystallization and flowability. Table 2 shows summary of theobservations.

TABLE 2 Coupon Day Corrosion Composition Tested (54 C.) −12 C. stabilityStock solution 28 days Corroded Small amount (no additive) overnight ofcrystals formed overnight Stock (99%) + 28 days No corrosion HomogeneousAMP-95 (1%) solution Stock (99%) + Quinaldine 28 days No corrosion Smallamount (1%) of crystals Stock (98.5%) + 18 days No corrosion Smallamount Epoxidized linseed of crystals oil (1%) + AMP 95 (0.5%)* Stock(98.5%) + 18 days No corrosion Small amount Epoxydecane of crystals(1%) + AMP 99 (0.5%) Stock (98.5%) + 18 days No corrosion Small amountEpoxidized linseed of crystals oil (1%) + Methyl Nicotinate (0.5%) Stock(98.5%) + 18 days No corrosion Homogeneous Epoxydecane solution (1%) +Methyl Nicotinate (0.5%)

Example 3

Homogeneous compositions of nitrapyrin technical grade (90%, 360 g/L)were made in different ratios of mixture of cyclopentanone orcyclohexanone and Rhodiasolv RPDE (mixture of dimethyl glutarate,dimethyl adipate and dimethyl succinate). A small quantity (˜15 mL) ofthe solution in glass jars were left for storage stability evaluation atroom temperature (˜20 C) and −10 C. The −10 C sample was seeded after itreached 24 hrs age by incorporating few small grains of nitrapyrintechnical in the cold solution and was immediately stored back to the−10 C temperature. The solutions at different temperatures were observedfor any inhomogeneity, crystallization and flowability. No crystals orany other inhomogeneities were observed in the solution at anytemperatures within 2 weeks of storage. Table 3 shows a summary of thecompositions and their stability.

TABLE 3 Composition (360 g/L Nitrapyrin Stability at room temperaturetechnical in solvent mixtures) and −10 C. Cylcopentanone/RPDE (60-40 wt%) Homogeneous solution Cylcohexanone/RPDE (60-40 wt %) Homogeneoussolution Cyclopentanone Homogeneous solution Cyclohexanone Homogeneoussolution

Corrosion Tests:

A stock solution of 360 g/L nitrapyrin technical grade incyclohexanone/RPDE (60:40 weight ratio) was prepared and corrosioninhibitors in specific amounts were added to this solution. Theresultant solutions were tested for corrosion issues with carbon steeltanks using following protocol. A carbon steel coupon was partiallysubmerged into the solution stored at 54 C. The coupon was periodicallyobserved for any sign of corrosion in liquid and vapor phases. Table 4shows a summary of the observations.

TABLE 4 Composition Coupon appearance Stock (no corrosion inhibitor)Corrosion in liquid and vapor phase overnight 98.5 wt % Stock + 1.0 wt %No sign of corrosion in liquid Epoxydecane + 0.5% Nicotinamide or vaporphase for duration of observation (45 days) 98.5 wt % Stock + 1.0 wt %No sign of corrosion in liquid Epoxydecane + 0.5% 1-methyl or vaporphase for duration of Imidazole observation (18 days) 97.0 wt % Stock +1.0 wt % No sign of corrosion in liquid phase Nicotinamide + 2.0 wt %and slight corrosion in vapor phase epoxidized linseed oil for durationof observation (90 days); test conducted at 50 C.

Example 4

Storage stability tests: Homogeneous composition of nitrapyrin technicalgrade (360 g/L) was dispersed in methoxybenzene solvent, and a quantityof about 15 mL of the solution in glass jars were left for storagestability at room temperature (˜20° C.), 54° C. and −7° C. The −7° C.sample was seeded after it reached 24 hrs age by incorporating few smallgrains of nitrapyrin technical in the cold solution and was immediatelystored back to the −7° C. temperature. The solutions at differenttemperatures were observed for any inhomogeneity, crystallization andflowability. No crystals or any other inhomogeneities were observed inthe solution at any temperatures within 2 weeks of storage.

Corrosion tests: A stock solution of 360 g/L nitrapyrin technical gradein methoxybenzene was prepared and corrosion inhibitors in specificamount were added to this solution. The resultant solutions were testedfor corrosion issues with carbon steel tanks using following protocol. Acarbon steel coupon was partially submerged into the solution stored at54° C. The coupon was periodically observed for any sign of corrosion inliquid and vapor phases. Table 5 shows summary of the observations.

TABLE 5 Composition Coupon appearance Stock (no corrosion inhibitor) Nosign of corrosion in liquid or vapor phase until 45 days; latercorrosion in vapor phase 98.5 wt % Stock + 1.0 wt % Methyl No sign ofcorrosion in liquid Isonicotinate + 0.5% AMP-95 or vapor phase forduration of observation (70 days) 99.0 wt % Stock + 0.5 wt % No sign ofcorrosion in liquid Nictotinamide + 0.5% AMP-95 or vapor phase forduration of observation (70 days) 99.0 wt % Stock + 0.5 wt % No sign ofcorrosion in liquid Nictotinamide + 1% Epoxydecane or vapor phase forduration of observation (24 days)

While the novel technology has been illustrated and described in detailin the figures and foregoing description, the same is to be consideredas illustrative and not restrictive in character, it being understoodthat only the preferred embodiments have been shown and described andthat all changes and modifications that come within the spirit of thenovel technology are desired to be protected. As well, while the noveltechnology was illustrated using specific examples, theoreticalarguments, accounts, and illustrations, these illustrations and theaccompanying discussion should by no means be interpreted as limitingthe technology. All patents, patent applications, and references totexts, scientific treatises, publications, and the like referenced inthis application are incorporated herein by reference in their entirety.

We claim:
 1. A formulation, comprising: an inhibitor of nitrification;at least one corrosion inhibitor; a polar solvent capable of dissolvingthe nitrification inhibitor; and a second solvent, the second solvent ismiscible in the polar solvent and wherein the second solvent is no morepolar than the first solvent.
 2. The formulation according to claim 1,wherein the at least one corrosion inhibitor is selected from the groupconsisting of: (a) methylpyridines:

(b) pyridine carboxamides:

(c) pyridine carboxylic acid and esters:

(d) epoxidized seed or vegetable oils:

wherein R₁, R₂, and R₃ independently represent C₁₄-C₂₀ alkyl groupssubstituted with from zero to four epoxide groups; (e) epoxy resinsbased on bisphenol-type chemistry:

wherein R₁ and R₂ independently represent H, C₁-C₄ alkyl, or phenyl, andR₃ and R₄ independently represent H, C₁-C₄ alkyl, C₁-C₄ haloalkyl, orphenyl; (f) 1,2-epoxyalkanes:

(g) 1-alkylimidazoles:

(h) amine salts of nicotinic acid:

wherein R¹, R² and R³ independently represent H, (C₁-C₁₈) alkyl or(C₁-C₁₈) alkyl substituted with one or more substituents selected from,but not limited to, halogen, hydroxy, alkoxy or alkylthio, provided thatthe substituents are sterically compatible and the rules of chemicalbonding and strain energy are satisfied, or any two of R¹, R² and R³represent —(CH₂)_(n)— where n is an integer from 3-5; (i) primary,secondary & tertiary amines:

wherein R¹, R² and R³ independently represent H, (C₁-C₁₈) alkyl or(C₁-C₁₈) alkyl substituted with one or more substituents selected from,but not limited to, halogen, hydroxy, alkoxy or alkylthio, provided thatthe substituents are sterically compatible and the rules of chemicalbonding and strain energy are satisfied, or any two of R¹, R² and R³represent —(CH₂)_(n)— where n is an integer from 3-5; (j) tertiary amineoxides:

wherein R⁴, R⁵ and R⁶ independently represent (C₁-C₁₈) alkyl or (C₁-C₁₈)alkyl substituted with one or more substituents selected from, but notlimited to, halogen, hydroxy, alkoxy or alkylthio, provided that thesubstituents are sterically compatible and the rules of chemical bondingand strain energy are satisfied, or any two of R¹, R² and R³ represent—(CH₂)_(n)— where n is an integer from 3-5, or wherein R⁴ is a straightor branched chain (C₁-C₁₈) alkyl or an alkyletherpropyl oralkylamidopropyl of the formula:

wherein R⁷ is a straight or branched chain (C₁₀-C₁₈) alkyl, and R⁵ andR⁶ independently are straight or branched chain (C₁-C₁₈) alkyl orethoxylates or propoxylates of the formula:

wherein n is an integer from 1 to 20; (k) tetra-substituted ammoniumsalts:

wherein R¹, R² and R³ independently represents (C₁-C₁₆) alkyl or(C₁-C₁₈) alkyl substituted with one or more substituents selected from,but not limited to, halogen, hydroxy, alkoxy or alkylthio, provided thatthe substituents are sterically compatible and the rules of chemicalbonding and strain energy are satisfied, or any two of R¹, R² and R³represent —(CH₂)_(n)— where n is an integer from 3-5, R⁴ represents((C₁-C₁₆) alkyl or arylalkyl), and X⁻ is selected from, but not limitedto, chloride, bromide, or iodide; and mixtures thereof.
 3. Theformulation according to claim 1, wherein the polar solvent is a ketoneselected from cyclopentanone and cyclohexanone.
 4. The formulationaccording to claim 1, wherein the polar solvent is a dibasic ester whichcomprises: a diester of formula (IIa):

a diester of formula (IIb):

and a diester of formula (IIc):

wherein R₁ and R₂ individually comprise a hydrocarbon having from 1 toabout 8 carbon atoms.
 5. The formulation according to claim 1, whereinthe polar solvent is an organophosphate compound selected from the groupincluding triethyl phosphate, tri(isobutyl)phosphate, tributoxyethylphosphate and tris(2-ethylhexyl) phosphate.
 6. The formulation accordingto claim 1, wherein the polar solvent is an alkoxybenzene compoundselected from methoxybenzene and ethoxybenzene.
 7. The formulationaccording to claim 1, comprising: about 250 to about 300 g/L of2-chloro-6-(trichloromethyl)pyridine; about 40 to about 60 weightpercent of a mixture of N, N-dimethyloctanamide (N,N-dimethylcaprylamide) and N, N-dimethyldecanamide(N,N-dimethylcapramide); about 0.5 to about 1.5 weight percent of liquidepoxy resin and about 0.5 to about 1.5 weight percent 2,6-dimethylpyridine; and about 5 to about 20 weight percent solventnaphtha.
 8. The formulation according to claim 1, comprising: about 230to about 300 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 45 toabout 55 weight percent of a mixture of N, N-dimethyloctanamide (N,N-dimethylcaprylamide) and N, N-dimethyldecanamide (N,N-dimethylcapramide); about 0.75 to about 1.4 weight percent of liquidepoxy resin; about 0.5 to about 1.5 weight percent 2,6-dimethylpyridine; and about 10 to about 15 weight percent solventnaphtha.
 9. The formulation according to claim 1, comprising: about 240g/L of 2-chloro-6-(trichloromethyl)pyridine; about 50.0 to about 55weight percent of a mixture of N,N-dimethyloctanamide(N,N-dimethylcaprylamide) and N,N-dimethyldecanamide(N,N-dimethylcapramide); about 1.0 to about 1.1 weight percent of liquidepoxy resin oil; about 0.5 to about 1.5 weight percent 2,6-dimethylpyridine; and about 11.0 to about 14.0 weight percent solventnaphtha.
 10. The formulation according to claim 1, comprising: about 240g/L of 2-chloro-6-(trichloromethyl)pyridine; about 50.55 weight percentof a mixture of N, N-dimethyloctanamide (N,N-dimethylcaprylamide) and N,N-dimethyldecanamide (N, N-dimethylcapramide); about 1.2 weight percentof liquid epoxy resin oil; about 0.5 to about 1.5 weight percent 2,6-dimethylpyridine; and about 12.64 weight percent solvent naphtha. 11.The formulation according to claim 1, comprising: about 200 to about 400g/L of 2-chloro-6-(trichloromethyl)pyridine; about 20 to about 50 weightpercent of a dibasic ester; about 0.5 to about 2.5 weight percent ofepoxidized linseed oil; about 0.5 to about 2.5 weight percent ofnicotinamide; and about 20.0 to about 50.0 weight percent ofcyclohexanone.
 12. The formulation according to claim 1, comprising:about 240 g/L to about 350 g/L of 2-chloro-6-(trichloromethyl)pyridine;about 20 to about 40 weight percent of a dibasic ester; about 1.5 toabout 2.5 weight percent of epoxidized linseed oil; about 0.5 to about1.5 weight percent nicotinamide; and about 25.0 to about 45.0 weightpercent cyclohexanone.
 13. The formulation according to claim 1,comprising: about 240 g/L of 2-chloro-6-(trichloromethyl)pyridine; about50.47 weight percent of a dibasic ester; about 1.5 weight percent ofepoxidized linseed oil; about 0.8 weight percent nicotinamide; and about12.62 weight percent cyclohexanone.
 14. The formulation according toclaim 1, comprising: about 200 to about 400 g/L of2-chloro-6-(trichloromethyl)pyridine; about 40 to about 60 weightpercent of a dibasic ester; about 0.5 to about 2.5 weight percent ofepoxidized linseed oil; and about 0.4 to about 1.5 weight percentnicotinamide.
 15. The formulation according to claim 1, comprising:about 240 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 63.08weight percent of a dibasic ester; about 1.5 weight percent ofepoxidized linseed oil; and about 0.6 to about 1.0 weight percentnicotinamide.
 16. The formulation according to claim 1, comprising:about 240 g/L of 2-chloro-6-(trichloromethyl)pyridine; about 63.08weight percent of a dibasic ester; about 1.5 weight percent ofepoxidized linseed oil; and about 0.8 weight percent nicotinamide.
 17. Aformulation, comprising: about 324 g/L of2-chloro-6-(trichloromethyl)pyridine; about 26.02 weight percent of adibasic ester; about 2.04 weight percent of epoxidized linseed oil;about 0.98 weight percent nicotinamide; and about 39.02 weight percentcyclohexanone.
 18. A formulation, comprising; the formulation accordingto claim 17; and at least one additional agricultural ingredientselected from the group consisting of: herbicides, insecticides,mitocides, fungicides, and fertilizers.
 19. The formulation according toclaim 18, wherein the agricultural ingredient is a fertilizer.
 20. Theformulation according to claim 19, wherein the fertilizer includesnitrogen.
 21. A method for treating soil, comprising the steps of:applying at least one of the formulation of claim 17 to at least onearea selected from the area consisting of: the surface of a portion ofsoil, beneath the surface of a portion of soil, a portion of a plant,and a portion of a surface adjacent to a plant.
 22. The method accordingto claim 21, wherein the applying step includes injecting theformulation into a portion of soil.